JPS5861178A - Desulfurization demetallization denitrogenation for coal or coal liquid raw material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] This invention relates to the treatment of coal or stone liquids.

j! In detail, this invention converts coal into sulfur from coal liquid,
Concerning contact treatments for the removal of nitrogen and metal compounds.

This invention produces manganese nodules from coal or coal liquid raw materials containing sulfur impurities without adding hydrogen.

A sulfur-impure-containing coal is produced by contacting it with a catalyst consisting of a naturally occurring porous metal ore selected from the group consisting of swampite, swampmanganese and nickel-coated metal ore, and a hydrogen donor solvent. , provides a method for desulfurizing, demetallizing and denitrifying raw materials.

It is well known to use a decoupling system for decoupling petroleum fractions.
No. t is the hydrocarbon fraction J40f-jdeqC<zoo”p
discloses the removal of sulfur by contacting with manganese hydroxide or hydrated manganese oxide at a temperature of ~710 a). U.S. Patent 952. JJD, No. 094 Komangan baby boomer (
Describes the removal of sulfur compounds from gas sinter using Nodew h) tllE. U.S. Patent No. s.ti.
-J numbers disclose desulfurization, denitrification, and hydrogenation processes in which manganese nodules are useful as catalysts. US 13III Patent No. J
J 09,0 Tei No. 7 is cracked by ion-exchanging manganese nodules with hydrogen ions.

Compositions useful in hydrocarbon conversion reactions such as hydrocracking, oxidation, olefin hydrogenation, and isomerization are disclosed. U.S.S% Permit No. J, t t J, Oj
No. O, No. J, T/J, and J J/ are typical examples of demetallization and desulfurization using manganese nodules from petroleum residue.

It is also known that ferrous compound pipes are useful in desulfurizing coal. U.S. Patent No. J, 909. Co/J discloses the use of metal chloride salts, such as ferric chloride, as capable of dissolving sulfur-containing organic compounds in coal. No. 3,741,911 uses ferric ions to round off pyritic sulfur from coal. U.S. Patent No. 3,
999.9! issue discloses the reaction of coal with ferromagnetic particles to remove sulfur.

According to the present invention, the desulfurization, demetallization and denitrification treatment of coal or coal liquid raw materials is carried out by adding hydrogen from the outside to the raw materials to produce manganese nodules, swamp iron ore, swamp manganese% and wire nickel red (nickel ladelite). This is carried out by contacting a catalytically effective amount of a naturally occurring porous metal ore, such as, with a hydrogen donor solvent.

Since the reserves of coal are large compared to the reserves of liquid petroleum, the conversion of coal into liquid fuel and gaseous melt is constantly increasing in importance. The quality liquid is of low quality because it has a low hydrogen content and a high content of petro atoms. These residual oils can be used as boiler fuel! or economically more i
Fresh oil and pure coal products KII will be catalytically upgraded. However, metal contamination in the catalytic conversion of coal.
Requires a catalyst that is less susceptible to poisoning. j! The large amounts of sulfur, nitrogen and oxygen contained in the coal significantly reduce the overall activity of the catalyst. Various water bulking desulfurization methods have been proposed, but all of these methods consume large amounts of hydrogen and are therefore expensive.

In the method of this invention, without adding water volume from outside,
And in the presence of hydrogen donor solvent & desulfurization, demetalization and denitrification of coal! A simple and inexpensive catalyst has been found that can be used. This catalyst is incan nodules, swamp iron ore, and swamp manganese! 1 consists of a naturally occurring porous metal ore such as nickel lag 2ite. These materials can be obtained in expanded quantities and are relatively inexpensive. Furthermore, such ores can effectively desulfurize and denitrify coal raw materials, and can also remove metal impurities.

The economic trap of this method of coal processing is that the porous catalysts become inactive due to p-contamination during use, and their disposal is not very effective since they are of low cost. .

Manganese nodules are known as K.

It is a naturally occurring deposit found on the ocean floor consisting of manganese along with other metals including iron, cobalt, nickel and steel. They are found in large quantities on the ocean floor and lake bottom. For example, they are abundant on the ocean floors of the Pacific and Atlantic oceans and on the lakebeds of Lake Michigan. Manganese nodules are characterized by a large surface area, i.e., a surface area greater than t z o s”/g. These nodules come in various shapes, but most are obtained from the ocean and are shaped like potatoes. Those obtained from the bottom of fresh water, such as the bottom of Lake Michigan, tend to be smaller in size than those from the ocean floor, depending on the relative amounts of manganese and iron they contain. It is clayey and has a black to brown color. It is porous and has a light nitrogen content, with an average specific gravity of about -1.

Generally, their i diameter is 0. Jko (to) ~ Koko9aIl, but the length/J, JIB, direct@ti, tei (to)
So, the weight? I wonder if it will reach J#? To with a big 40 trench
For.

In addition to the metals mentioned above! Shigan Dandan Hiro silicon, aluminium, calcium and magnesium and a small amount of molybdenum, zinc%! Also contains 1% vanadium and rare earth elements.

Chemical and physical properties of manganese nodules as catalysts for desulfurization of hydrogen raw materials This is quite different from the conventional catalyst components used. The baby boom line is about ioo~-z Own”/i (D has a high surface area, but the surface area decreases due to metal deposition during the hydrodesulfurization reaction.
@riaanMin*ra1. ogiat ) J j
/ Volume (/lA & Cow) 191~! Rog@r Tsui Burns and D,W, Fu@
rgtsnau) by [Electroton-Globe Middle Teter (Nessian Off-Inter-Element Relay Enships In-kai Mangan “Nobu Tame-ru”)
As shown in Figure 2, the concentrations of the various 0* groups contained in the nodule, namely mankan, iron, cobalt, steel, and nickel, are not uniform throughout the crystal structure of the nodule, but are rather distributed in the lateral direction of the nodule cross section. Concentrations of various metals vary markedly depending on location. However, there appears to be a correlation between iron and cobalt concentrations. On the other hand, the catalysts that can be produced have the highest degree of uniformity that can be achieved by the manufacturer.

Manganese nodules can be used as desulfurization/tax II/denitrification catalysts for coal feedstocks substantially in their deep-seated state, ie, as deposited from the water bed in which they reside. The nodule can be used up to the time it is mined, optionally after cleaning to remove salt water and mud or loosely adhering material from the nodule surface.

The method of Jin's invention may also be carried out using pre-treated manganese nodules as a catalyst. Pre-treatment of the manganese nodules may include sulfurization or leaching treatment to remove one or more components from the nodules. I can pass.

Increase the degree of demetalization of manganese nodules sulfurization treatment raw material. This treatment also increases the degree of desulfurization.

Although Conradson reduces carbon residual (OOR).

Each of these has a heavy Ki1 weight and depth. This treatment is carried out, for example, by contacting the manganese nodules with a volume of sulfide water. * Hydrogen chloride may be pure or mixed with other gases.

However, the hydrogen sulfide should be substantially hydrogen-free. The sulfiding treatment temperature is from 1 to 1, and the time is from 1 to 1. Sulfurization treatment can be carried out, for example, by continuously passing a volume of sulfurized water over the manganese nodules during the sulfurization reaction.

Although there are no strict limits on the space velocity of hydrogen sulfide, it is appropriate to carry out the extraction at a space velocity commensurate with the equipment so that dry hydrogen sulfide is continuously detected in the exhaust gas stream.

The manganese nodules are also pretreated by a leaching station 11,
/II may contain one or more ingredients.

As mentioned above, manganese nodules contain copper, nickel and molybdenum in addition to manganese, and manganese nodules can be processed into steel, nickel or molybdenum, and any kind or three of these metals by pre-leaching treatment. can be excluded. It contains expanded manganese nodules, nickel and molybdenum in sufficient quantities to provide industrial resources. Furthermore, the at least partial removal of these metals and other metal components from mankan nodules does not have a detrimental effect on the catalytic activity of the nodules; thus, according to embodiments of the invention, copper, nickel, Molybdenum and other gold III can be recovered from the manganese nodules for economic benefit and the remainder of the manganese nodules can be used as a catalyst.

Steel and nickel removal may be accomplished by leaching the manganese nodules with an aqueous solution of strong acid.

Herein, strong acids and #'i mean hydrochloric acid, iron sulfur and nitric acid. Molybdenum thiomganese nodules can be removed from mankan nodules by leaching with an aqueous base solution such as sodium hydroxide or dithrium carbonate. These aqueous base solutions should have a pH of at least tq) pH 1, preferably at least 10. Leaching with an aqueous base solution can be carried out at the mass temperature or the boiling point of said aqueous solution.The type of operation in which the manganese nodules are crushed, sized and used with or without pretreatment, e.g. fixed bed. Desired particle size can be obtained according to operation trench, fluidized bed operation, etc.

After use and before catalytic loss, the spent catalyst can be used to recover valuable metals such as copper, nickel, etc. It can also be used to recover other components.

Another naturally occurring porous metal ore that can be used in the desulphurization/demetallization/denitrification process MK is a loose mono-agglomerated ore obtained from wetlands known as swampite.

It is a variety of limonite (J'Ht'), a naturally occurring ferrous oxide containing approximately 60% iron by weight.It is yellow to brown in color and similar to other iron ores. Iron ore is an important ore commonly found in the United States and Europe, formed by oxidation and/or alteration due to water use.
'l/In addition, the surface area of ptOd or more, the hardness of j-, t, and j (basket male hardness), and the average density 3. ζ
The mixture is then crushed and dried to constant weight, i.

~-〇Mesh (American sieve series) K Sort.

Depending on the requirements, swamp iron ore may be leached or sulfurized in the same manner as shown for manganese nodules, or both.

Swamp manganese is another naturally occurring porous metal ore that can be used. This ore may also be pre-leached and subjected to sulfide treatment or both.Numamankan is similar to swampite;
It consists primarily of oxides of manganese and water, with some oxidation of iron, and also contains silica, alumina, and baryta. It is amorphous with a surface area of 10 to 71 or more, a Moos hardness of about 6, and a severity of JA of 3.4 to 10.

Swamp manganese and anhydrite are not considered to be separate ore types, but are colloidal manganese oxide containing various adsorbed impurities. Numa Mangan Welfare Yorotsu AK'
1lltB, Lake Superior in Lake Michigan - hematite deposits and tonal features.

/Q-79 or more, other suitable ores that can be used include nickel-containing 2ft ore. Silicate-type nickelites, such as common laterites and siliceous nickelites, are found in Southeast Asia, Cuba, Teecoslovakia, New Caledonia, Philippines, Indonesia, Greece, Yugoslavia, Guatemala and Venezuela. These ores usually contain free and bound water and on a dry basis less than J weight S of nickel, 0. /1 wt. - less than or equal to cobalt and 73 wt.
The above iron O analysis values are shown.

The alternative analytical values for laterite ore are as follows: Ni+Oo Ko, J Ko, 9
(as NiO) C /1.3
Koro, j (ha, as 0.) Or
/, ko /, ri (as Or, O,) M
gO/, t/j 810, J, tJ, tAI
,O,thing,! Da! 010 θ, / , 0. /LOI
／ ／j ／ ／、! OO nickel ore is ideally suited as a catalyst for the process of this invention and can be used directly in as-mined condition without further upgrading treatment. If desired, these ores can be pretreated by leaching or sulfurization or both treatments as described above. The desulfurization/demetalization/denitrification operations are carried out in the presence of a hydrogen donor solvent. The weight ratio of solvent and coal is 0! An amount of coal and solvent of ~t:/%, preferably about -2:/% is used. Hydrogen donor solvents are well known, and suitable hydrogen donor solvents include hydrogenated aromatic, nandene-aromatic compounds such as hydronaphthalene, eg, tetrali/, hydrotrace/, and hydro7ena/tre/. I can do it.

Compounds having at least one, preferably co or three or V aromatic nuclei, partially hydrogenated so as to contain an aromatic resonance, and containing an olefinic bond are excellent hydrogen donors. Helpful. Completely aromatic structures are not effective as hydrogen donors. Fully hydrogenated fused ring molecules have a small tendency to wing migration.Hence, the hydrogen donor partially hydrogenates the polynuclear aromatic to introduce an average of 7 to 3 hydrogen molecules and at least 7 partially hydrogenated molecules. By leaving a ring of individuals, it is preferentially emitted.

It is to be understood that the hydrogen donor solvent can be obtained from any source. Particularly valuable are the solvents available from coal processing systems, e.g. ? 'C~pgko''C(yro~too
°F), preferably 0°C to 31°C (WOO to 0°C)
It is an intermediate stream obtained from a coal liquefaction process that boils at 0°F. This type of intermediate stream consists of hydrogenated aromatics, naphthenic hydrocarbons, phenolics and similar compounds, containing at least 30% to 50% by weight of compounds known to be water donors. Including @ e.g. U.S. Patent No. 3. Please refer to 'yvi issue in tW. The water bulk donor solvent can be regenerated externally, for example by catalytic reduction, and optionally recycled. The recycled donor solvent need not be pure hydrogen donor or a mixture thereof, but may be substantially diluted with an inert solvent.

Other hydrogen-containing solvents can be used in conjunction with petroleum or coal derived solvents or in combination with the solvents. Such substances include water-miscible and water-immiscible lower aliphatic alcohols such as methanol, ethanol, propatool,
Inglopanol; butanol, pentanol, hexanol: Fatty alcohols such as cyclohexanol and ethers such as dimethyl ether.

Diethyl ether.

The desulfurization/demetallization/denitrogenation reaction is carried out by bringing the raw material coal into contact with a catalyst in the presence of a hydrogen donor solvent.
! The temperature used is 44℃ (a
go ~1 ozo°F), preferably 3 h 3°C ~ ptj
'c(6tσ~t!O''p). The amount of catalyst used can vary over a wide range, and the amount commonly used is 0 J - 100 wt. The raw coal together with the solvent may be passed up a solid bed of catalyst in a riser reactor or down a solid bed of catalyst in a down-flow trickle bed reactor. The reaction can also be carried out by passing the raw coal and solvent through a fluidized bed of catalyst.The reaction can also be carried out by contacting the raw coal, solvent and catalyst in a quarter reactor. can.

High volatile content and low volatile content prefix,! l Any solid carbonaceous material can be used as 'coal', including natural coals such as lignite, peat, or solvent-refined coals or related 'modified' coals. Coal is a viscous substance with a high ash, high metal and sulfur content. Even coals with poor cohesiveness are extremely suitable for this invention. The process of this invention is particularly useful for removing sulfur, which is the most difficult to remove to meet combustion specifications for naturally occurring or solvent refined coals.

Before use in the method of this invention, the coal is ground in a suitable mill, such as a hammer mill, to remove at least the SOX of the coal.
It is preferable to pass through a mesh (American sieve series). The ground coal is then dissolved or ground into a suitable solvent.

If desired, the solid carbon material may be recycled by conventional means known in the art prior to reaction for materials that are not converted to a liquid under the reaction conditions described herein. Various types of sulfur suitable for use with this invention /,7 JX
o, J t96 o, s 3% nitrogen
/j 3 XO, t IXO, 7lIN oxygen 7 kude I /! ! , 40z JJO41z charcoalz
go, tgz &! ,! Jz! Wjtz hydrogen j? , 3 J # j, Op j, Sanko 111 minutes λ,
? 71 j, wa9 # j
Although coal is the main material to be converted according to this invention, it is not necessary that it be a solid carbonaceous material to be converted, such as urban carp, rubber (natural or synthetic), etc. , cellulosic waste*, conventionally buried waste, burned waste or other waste polymers that have been disposed of from other sources.
~j0% by weight can also be used in addition to the raw material coal. Organisms defined as renewable carbon sources, such as grasses, grains, trees, seaweed (curzo) and other marine plants, are also included in solid R-potential materials. The addition of such materials to this process increases the yield of valuable liquid fuel products from low cost, readily available materials that would otherwise have to be discarded.

This invention will be explained below by giving examples of the best mode for carrying out the invention.

Example 7 ~ Example Furnace A TiC, 300 Ct, stainless steel autoclave was heated with short contact time solvent refined coal (Example 1 ~ Example -) and Monterrey coal (Example 5) as shown in Table 3 below.
The raw material for the bait in Examples 1 to 1, which was charged as a raw material in 1 ml, is completely soluble in tetrahydrofurinated fluoride. The amounts of hydrogen donor solvent and catalyst (if used) as shown in Table 3 were added. The autoclave was closed, pressure tested with argon, charged with argon at LA/atmosphere and heated under stirring to the temperature shown in Table 1 for 7 to 1 hour. The system was kept under agitation and autogenous pressure at the temperatures and times indicated in the table.

It was then forced to cool down for 1 minute by passing water through a cooling coil in contact with the contents of the autoclave.
The autoclave was opened, the contents were washed out with tetrahydrofuran, the catalyst was slightly extracted with tetrahydrofuran in a Soxhlet, and the extract was added to the other contents. The solvent was then removed on a rotary evaporator and the residue was distilled under reduced pressure to yield a 3<0>C solvent-purified product.

example! In this example, Mont@r@7 coal (MT) was similar to the raw material from which the solvent-extracted stone legs of Examples 1 to 2 were obtained. Contains sulfur. In this example, approximately -sl of coal is mixed with a synthesis solvent (~-2Xr-
Picoline, “XP/Vsol, @1X Tetralin%
ztNJ-Methylnaphthalene) was injected as a slurry with a width of about J:1 into the same mixture of preheated solvent. The resulting mixture was mixed with G<! 7℃(zaoo″F) J 9 J
kPa (day, HE (4 hire 2 (/3.y3psi)
) under hydrogen pressure with stirring for 90 minutes.

The mixture was quenched and worked up as described above, except that pyridine was used for extraction. The ratio of S, S:coal was 6:/.

Table 3 0 ヂ, 31・7 M /J /, 0・8 V, t //J Ash content 0. l- aromatic ring -- 1/JX=crystalline alkaline compound known as faujasite.

, 2 Mn 1104: 1 ngan nodules @/see table J MsOH-methanol O ri, ri M /J 8 /, de 0, // BNO= fli1MIKIII coal J
Hiroshi
31 hours 1 hour
90 minutes t*3yv(aobr) 5t
sb (zso) de Jya (tssJ)
CH*)! Sodium form of silicate: /, 3t%--Methylnaphthalene From Table 3, the best desulfurization is without H3 Example 31 Example tI) FC
It can be seen that manganese nodules are obtained in a hydrogen donating solvent (methanol or tetrali/). In this case, N, O, and ash (metallic) components were also significantly reduced. The yield was low and the desulfurization was negligible for the (7 augia sai) Na type)/jX molecular sieve (Example 1). In the blank reaction (no catalyst, Example J), the yield was low and desulfurization was insufficient. Example j is a suitable experiment for comparison. After all, the experimental raw material for the other examples is 8RO (solvent purified right leg) produced during the experiment of Example S in about 1 minute.
from trout. In this example, desulfurization from 7.91 wt.% to S wt.% was achieved even with tetralin and in the presence of hydrogen and coal minerals as a potential catalyst. do not have. To pass current boiler fuel specifications, the sulfur content must be approximately 0. The weight must be ~.

The manganese nodules obtained in Example J and Example 1 were collected from the ocean floor of the Pacific Ocean. After collecting these nodules from the seabed, they were washed with salt water and 1 m of water.

It was then ground, leached with boiling water for 5 minutes, dried at 100° C. to constant weight, and sieved through 1-30 mesh (American standard sieve series) K11 gll. This nodule had the physical characteristics and chemical composition of the queen: No. +l! ! Surface area 7f J Jtsu Stomatal diameter [O/Gestrom■] SJ Stomatal volume (CIrL”/l) o,
Reference JA Manganese (Mn) (Weight jg')
Jj, σ iron (Fθ) (11 quantity X)
/! , 0 nickel (Ni) (weight X)
<o, ot 1st oxidation cohar) (000) (weight x
) <o, op molybdenum trioxide (MOO,) (weight
Swamp iron ore obtained from (Batsto) is washed to remove mud and other loosely adhered materials, then crushed and
It was dried to a constant weight and sized with 30 mesh (US sieve series) K. This sized particle jIt-solvent refined coal (moretele-short contact time coal)! 1% solvent TSL (methanol coj and 11 methylnaphthalene 5 oil
), and the resulting mixture is φkot"c<too'F
) Heated for KJ hours. After cooling, the reaction mixture was diluted with tetrahydro7
The nickel catalyst was extracted with tetrahydrofuran, the extract was added to the other liquor, the solvent was removed by evaporation, and then distilled to obtain a solvent refined coal product with reduced sulfur, nitrogen and ash content.

Example 7 The analytical values of telite nickel ore from New Caledonia are as follows: Weight % N1 831 Co O, 09 all re #/J MgOj, 5 M20II4Iλ! Sin, ri, da 0 cases/~
The nickel ore was washed free of mud and other loosely adhered materials according to the procedure described in Example JK. The ore was crushed, dried at 100° C. to a constant weight, and sized using Komatsu K (American sieve series). This sized ore sli is purified by solvent refining hexapod (Monterrey short contact time coal) II and solvent 7jy.
(Methanol co-sl and 11-methylnaphthalene 5op)
and the resulting mixture was heated to 7° C. for 1 hour. After cooling, one reaction mixture is washed with tetrahydro 7 run, the nickel catalyst is extracted with tetrahydrone 2/, this extract is added to the other solution, the obtained solvent is removed by evaporation, and the residue is distilled. A solvent refined coal product with reduced sulfur, nitrogen and ash content was obtained.

Claims (1)

[Scope of Claims] l Coal containing sulfur is a liquid coal raw material,
Hydrogen donor solvent and manganese nodules in the absence of added hydrogen, swamp iron ore, swamp! 1. A process for desulfurization, demetalization and denitrification of sulfur impurity-containing coal or liquid coal raw materials, characterized by contacting them with a catalyst consisting of a naturally occurring porous metal ore selected from the group consisting of carbon dioxide and nickel tucrite. λ The method according to claim 1, wherein the porous metal ore is swamp iron ore. 3. The method according to claim 1, wherein the porous metal ore is grown in a swamp. 8. The method according to claim 7, wherein the porous metal ore is nickel tucrite. The method described in paragraph 1 of the patented OSS, wherein the porous metal ore is an underwater sedimentary material known as manganese nodules. The method according to any one of claims 1 to 1, wherein the porous metal ore is pre-sulfurized before leaching. Z The temperature of the manganese nodules is at least JC and 100
1,000,000 parts per Jl) 1oao @ or less 0 total soil content of water can approach the nodules! II. Claims 1 to wi4 using a product that has been washed for a sufficient period of time to increase the area.
The method described in any of the paragraphs. l The scope of **et* described in paragraph S, where the manganese nodules contain steel, nickel t or molybdenum in their composition and at least a part of the steel, nickel or molybdenum content has been removed. the method of. A method as claimed in claim 1, wherein the manganese nodules are leached with an IIO aqueous solution and the manganese nodules from which a portion of the steel or nickel content has been removed are used. /(2 Leaching manganese nodules with basic water fB solution K
The method according to claim 1, which uses manganese nodules from which at least part of the molybdenum content has been removed. The method according to claim 1O, wherein the pH of the aqueous solution of the base is at least t. The method according to claim 1, wherein the pH of the aqueous solution of the base is at least 10%.